CS212783B2 - Photopolymerizable material - Google Patents

Abstract

A photopolymerizable material suitable for use in the production of lithographic printing plates comprises a polymer which includes a plurality of structural units represented by the Formula: <IMAGE> in which R1 represents a hydrogen atom or a methyl group; R2 represents a hydrogen atom, an alkyl or substituted alkyl group, an aryl or substituted aryl group, or a heterocyclic or substituted heterocyclic group; R3, R4 and R5, which may be the same or different, each represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an aralkyl group, an aralkoxy group or an alkoxy carbonyl group; Z represents a hydroxyl group, or an ester group and a is an integer greater than or equal to 1. The polymer may be produced by reacting a polymer of 2,3-epoxy propyl acrylate or 2,3-epoxy propyl methacrylate with an acid of formula <IMAGE>

Description

The invention relates to a photopolymerizable material consisting of a polymer comprising structural units of the general formula

R1

I r-C-CH—

C = O

I o

AND.

CH2

CH — ZR

II

CH 2 —O — C — C = C- (CR4 = CR3) _and —R 2 (II

O COOH

This material is soluble in aqueous solutions of inorganic salts in uncured form. In particular, the photopolymerizable material may be used for the photomechanical production of printing plates and photoresists. .

The invention relates to a photopolymerizable material.

Numerous photosensitive compositions are known which are based on solvent-soluble photosensitive polymers, such as cinnamic acid polyvinyl ester.

A disadvantage of these known compositions is that when applied, for example, as a layer on a suitable substrate to form a printing plate or photoresist, after the curing reaction due to actinic radiation exposure, expensive and possibly toxic and / or incendiary materials need to be used. solvents to remove uncured areas.

The above-mentioned drawbacks have no photopolymerizable material according to the invention, which consists in that it consists of a polymer containing units of the general formula I

R ¹ —C — CH ₂ -

C = O

O

AND

CHž

CH — ZR ⁵

CH 2 -O-C-C = C- (CR 4 = CR ³ ) _and R ² * II I

About COOH (I) in which

R1 represents a hydrogen atom or a methyl group,

R ² represents a hydrogen · atom, an alkyl · optionally substituted by a chlorine atom or an aryl group or an alkoxy group and having 1 to 10 carbon atoms, an aryl group optionally substituted with a halogen atom · or an alkyl group or · an alkoxy group and having a · 6 to 10 carbon atoms or a heterocyclic group optionally substituted with a halogen atom, an alkyl group, an aryl group or an alkoxy group and having from 3 to 9 carbon atoms,

R ³ , R 4 and R ⁵ , which may have the same or different meanings, represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms 1-0 carbon atoms, aryloxy of 6 to 10 carbon atoms, aralkyl of 7 to 20 carbon atoms, aralkoxy of 7 to 20 carbon atoms or alkoxycarbonyl of 2 to 11 carbon atoms,

Z represents a hydroxyl group or an ester group derived from an aliphatic, aromatic or heterocyclic carboxylic acid, its halide or anhydride. and a is 1.

The photopolymerizable material of the invention is preferably a polymer comprising the structural units of formula (I) in which:

R2 is phenyl and

R 3, R 4 and R ⁵ are hydrogen, or

R 2 represents a 2-nitrophenyl group and

R 3, R 4 and R 5 represent a hydrogen atom, or

R 2 represents a 3-nitrophenyl group or or

R 3, R 4 and R 5 represent a hydrogen atom, or

R2 represents a phenyl group,

R 3 represents a chlorine atom and

R 4 and R 5 represent a hydrogen atom, or

R2 is 4-nitrophenyl,

R 3 represents a chlorine atom and

R4 and R5 are hydrogen.

The photopolymerizable material according to the invention may also consist of a polymer also comprising structural units of the general formula II

R ¹

I — C — CH2—

C = O

AND

O

I.

CHž. and

CH — Z ¹ OR

I IIi

CH 2 —O — C — C = C— (CR 4 = CR ³ Jb-R ²

R ⁶ (Π] in which

Z ¹ represents a hydroxyl group, a halogen atom or an ester group derived from an aliphatic, aromatic or heterocyclic carboxylic acid, its halide or anhydride,

R ¹ represents hydrogen or methyl,

R2 represents a hydrogen atom, an alkyl group optionally substituted by a halogen atom or an aryl or alkoxy group and having 1 to 10 carbon atoms, an aryl group optionally substituted by a halogen atom or an alkyl or alkoxy group and having a 6 to 10 carbon atoms, or a heterocyclic a group optionally substituted by a halogen atom, an alkyl group, an aryl group or an alkoxy group and having 3 to 9 carbon atoms,

R ³ , R ⁴ , R 5 and R ⁶ , which may have the same or different meanings, represent a hydrogen atom, a halogen atom, a cyano group, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 up to 10 carbon atoms, an aryloxy group having from 6 to 10 carbon atoms, an aralkyl group having from 7 to 20 carbon atoms, an -alkoxy group having from 7 to 20 carbon atoms, or an alkoxycarbonyl group having from 2 to 11 carbon atoms; 0 or 1.

The photopolymerizable material of the invention may also consist of a polymer comprising structural units of formula II wherein b is 0 and

^R2, R5 and R6 -atom · atom or b is 0,

R 2 and R ⁵ are hydrogen-α

R 6 represents a methyl group, or B represents 0,

R2 is phenyl and

R 5 and -R 6 are hydrogen, or οι b is 0,

R2 is 4-methoxyphenyl,

R 5 represents a hydrogen atom and

R 6 represents a cyano group, or b represents 0,

R2 is 4-chlorophenyl,

R 5 represents a hydrogen atom - a

R 6 represents a phenyl group, or B represents 0,

R2 represents a 4-methylphenyl group,

R 5 represents a hydrogen atom and R 6 represents a phenoxy group, or b represents 0,

R ² is 4-azidofenylovou group,

R 5 is -hydrogen and

R 6 represents a cyano group, or b represents 0,

R2 represents a 2-furyl group and

R5 and R6 are hydrogen or b is 1,

R2 is phenyl and

^R3, R4 and R5 are: H and

R 6 represents a cyano group, or b represents 1,

R2 is phenyl,

R 3, R 4 and R 5 are -hydrogen and

R 6 is ethoxycarbonyl, or b is 1,

R2 represents a phenyl group,

R3 and R4 are -atom hydrogen,

R 5 represents a methyl group and

R 6 represents a cyano group.

The photopolymerizable material according to the invention may also consist of a polymer also comprising structural units of the general formula III

Ri

I — C — CH2 — i

c = o

I o I

CHž

CI-I — Z ¹

CH2-O-C-R7

II o (III) in which

R1 represents a hydrogen atom or a methyl group,

Z ¹ represents a hydroxyl group, a halogen atom or an ester group derived from an aliphatic, aromatic or heterocyclic carboxylic acid, its halide or anhydride, and

R 7 represents an alkyl group optionally substituted by a halogen atom or an aryl or alkoxy group and having 1 to 10 carbon atoms, an aryl group optionally substituted by a halogen atom or an alkyl or -alkoxy group and having 6 to 10 carbon atoms, or a heterocyclic group- optionally substituted with a halogen atom or an alkyl group, an aryl group or an alkoxy group and having from 3 to 9 carbon atoms.

The photopolymerizable material of the invention is preferably a polymer comprising structural units of formula (III) in which:

R 7 represents a methyl group -a

Z 1 is a hydroxyl group, or

R 7 represents a heptyl group -a

Z 1 represents a hydroxyl group, or

R7 is ethyl and

Z ¹ represents a chlorine atom, or

R7 is trichloromethyl and

Z 1 represents a hydroxyl group.

The photopolymerizable material of the invention is preferably a polymer comprising also structural units derived from another unsaturated polymeric monomer.

The photopolymerizable material of the present invention is also preferably a polymer comprising units derived from methacrylic acid dodecyl ester, styrene or acrylic nitrile.

The advantage of the photopolymerizable material according to the invention is that it is not required to be expensive and possibly toxic and / or inflammable solvents, but only aqueous solutions of inorganic salts, to produce it after exposure to actinic radiation.

The polymer present in the material according to the invention can be formed by reacting a polymer of 2,3-epoxy-propylester of acrylic acid or of 2,3-epoxypropyl methacrylic acid ester (either homopolymers or copolymers of acrylic or methacrylic acid with, for example) one of the following: of the above monomers) with an ethylenically unsaturated dicarboxylic acid of the general formula IV

COOH

OF

R ² - '(CR 3 = CR ⁴ ) _O —C = CI'

R ⁵ COOH (IV) wherein a, R ² to R ⁵ are as defined above.

The sensitivity of the polymer according to the invention to actinic radiation is conditioned by double bonds, the solubility in alkali being given by unreacted carboxyl groups.

However, under appropriate conditions, it is possible to control the above reaction such that not all epoxy groups of the polymer from 2,3-epoxypropyl acrylic or methacrylic acid react with the dicarboxylic acid. It is then possible to react the unreacted units with an ethylenically unsaturated monocarboxylic acid (or the corresponding halide) of the formula

R2 - (CR 3 - CR ⁴ ) _{b -} C = C

I \

R 5 COOH (V) wherein b and R ² 'to R ⁶ have the meanings given above so that structural units of formula (II) and / or O' with a saturated carboxylic acid (or corresponding halide) of formula (VI) are formed

R ^{7 -} COOH, (VI) wherein R ⁷ is as defined above to form structural units of formula III. The structural units of formula II condition increased sensitivity to radiation without alkali solubility, and the structural units of formula III condition increased sensitivity to color.

Reacting the epoxy groups with acids or acid halides to produce structural units containing secondary hydroxyl groups or halogen atoms (in terms of the symbols Z ¹ and Z in formulas I, II and ^III-f). In cases where secondary hydroxyl groups are formed, they can advantageously react with a carboxylic acid or ester-forming derivative thereof, such as the corresponding acid halide or anhydride, thereby converting the secondary hydroxyl groups into ester groups. Reaction of the secondary hydroxyl groups with the acid units of the formula II (or with the derivatives of these ester-forming acids) results in increased radiation sensitivity, while using acids to form the structural units of the formula III (or derivatives of such ester-forming acids) achieves an increase in color perceptibility.

Thus, by varying the reactants and the reaction conditions, it is possible to produce phenolizable materials having different properties with respect to alkali solubility, radiation sensitivity, perceptibility, and crosstalk resistance.

To OOT - ^] ^ ^<1 ^^^^^ ^ ^{<^} ^ e ^ -rovateli lio material may be added dyes, pigments, leukobarviva, plastiOikátory · a / n · ebo sensitizers · whereupon it is possible to apply materials Ootopolymerovatelné on suitable substrates, such as aluminum, to prepare irradiation sensitive plates and suitable for subsequent exposure to light.

Further examples further describe the nature of the invention.

Some of the polymers and carboxylic acids used in the examples are prepared as described in the following syntheses:

Synthesis of AI

Methacrylic acid poly-2,3-epoxypropyl ester

A mixture of 8 g and ^{<-azodiistbutyr} tnitrilu · · ·, and 200 g of 2,3-epoxypropyl methacrylate · introduces slowly under nitrogen at 70 DEG C. into 400 ml of 2-butanone. The temperature is maintained for 3 hours and then raised to 80 ° C for 2 hours. The cooled solution is diluted by adding 1400 ml of 2-butanone, the diluted solution is poured into 12 liters of petroleum ether (b.p. 40-60 ° C), the precipitated product is filtered off with suction and dried to give 195 g of poly (methacrylic acid). epoxide equivalent of 158.7.

Synthesis of A 2

Poly-2,3-epoxypropyl ester of acrylic acid

A mixture of 0.36 g of α-azodiisobutyronitrile and 18.0 g of acrylic acid is slowly introduced under nitrogen at 0 DEG C. into a mixture of 60 ml of 2-butanone and 20 ml of ethanol. The temperature is maintained for one hour, then raised to 70 ° C for 2 hours and to 80 ° C for a further 2 hours. The cooled solution is diluted by adding 100 ml of 2-butanone, the diluted solution is poured into a liter of petroleum ether, b.p. 40 DEG -60 DEG C., the product is filtered off and dried to give 17.2 g of poly (2,3-epoxypropyl esters of acid). acrylic with epoxy equivalent.

Synthesis A 3

Copolymer of poly-Z + epoxypropyl methacrylic acid ester with methacrylic acid dodecyl ester

A mixture of 16.63 g of methacrylic acid 2,3-epoxypropyl ester, 3.31 g of methacrylic acid dodecyl ester, 0.4 g of dodecylthiol and 0.8 g of azodiisobutyronitrile is polymerized in 50 ml of 2-butanone using a described in Example A1 to give 15.2 g of the expected epoxy equivalent copolymer 178.2.

Synthesis A 4

Poly (2,3-epoxy) petroleum methacrylic acid copolymer with styrene

A mixture of 18.49 g of methacrylic acid 2,3-epoxypropyl ester, styrene (1.51 g), dodecylthiol (0.8 g) and 1 g, α'-azodiisobutyronitrile is polymerized in 50 ml of 2-butanone using the procedure described for Synthesis A 1 to give 18.4 g of the expected copolymer - about epoxide equivalent 171.

Synthesis A 5

Copolymer of poly-2,3-epoxypropyl acrylic acid and acrylic nitrile

A mixture of 20 g of 2,3-epoxypropyl acrylic acid, 0.92 g of acrylic acid nitrile, 0.4 g of dodecylthiol and 0.8 g of 1'-azodiisobutyronitrile is polymerized in a mixture of 50 ml of 2-butanone and 20 ml of ethanol using of the procedure described in Synthesis A 2 to give 20.1 g of the expected epoxy equivalent 145 copolymer.

Synthesis of B1 (i) 3-nitro-cinnamic acid aldehyde is prepared by condensing 3-nitrobenzaldehyde - with acetaldehyde according to Claisen and Schmitt as follows:

To a solution of 80 g (0.53 mole) of 3-nitrobenzyl aldehyde in 1.6 liters of ethanol was added 1.8 liters of water; Acetaldehyde (36 mL, 0.644 mol) was added followed by 10% aqueous sodium hydroxide (56 mL), followed by stirring at 20 ° C for 5 hours. Then the reaction mixture is decanted, the residue is boiled with 2 liters of 25% acetic acid solution, after cooling, the crude product is isolated by filtration (13.7 g) and used without any further purification as follows:

(ii) 3-η1ΐΓ00ίπη3ηινΗί16ηπΐΗ1οη-va was prepared by reacting 13.7 g of 3-nitro-cinnamic aldehyde with 8.05 g - (0.077 mol) of malonic acid in 20 ml of glacial acetic acid at 100 ° C for 6 hours. . After cooling, the precipitated product is filtered off, washed and dried to give 8.9 g of the expected product, m.p. 185-187 ° C.

Synthesis of B 2

Cinnamylidenemalonic acid is prepared by reacting 125 g (0.95 mol) of cinnamic aldehyde with 104 g (1 mol) of malonic acid in 200 ml of glacial acetic acid according to the procedure described in (ii) of Synthesis B1. mp 206-208 ° C.

Synthesis - B 3

2-Nitrocinnamylidenemalonic acid is prepared by reacting 100 g - (0.614 mole) of 2-nitro-cinnamic aldehyde with 100 g (0.96 mole) of malonic acid in 95 - ml glacial acetic acid according to the procedure described in Synthesis B 1; mp 185-187 ° C.

Synthesis of B 4 (i) / chlorocinnamic acid aldehyde is prepared using the following procedure:

To 40 ml of anhydrous dimethylformamide, 24 ml of the mixture was added slowly while cooling to 0 ° C, and stirred for 30 minutes. A solution of 24 g (0.2 mol) of acetophenone in 25 ml of anhydrous dimethylformamide is then added, and the reaction mixture is slowly added to the solution of phosphonium chloride. With stirring, the reaction mixture is allowed to rise to 20 DEG C., stirred at this temperature for 2 hours, poured into a stirred solution of 300 g of sodium acetate in 750 ml of water, stirred for a further 30 minutes. the product is extracted into ether, the ether solution is dried over anhydrous magnesium sulphate, and the ether is distilled off to give 28.8 g of crude product which is then used without further purification as described further below:

(ii) γ-Chlorcinnamyl acid ^: denmalonic acid was prepared by reacting 16.55 g of 3-hior cinnamic aldehyde with 10.4 g (0.1 mol) of malonic acid in 10 ml of glacial acetic acid using the procedure described above in synthesis B1 (ii) to give 7.5 g of the expected product, m.p. 158-160 ° C (dec.).

Synthesis of B5 (i) 4-Nitro- (3-chloro-cinnamic acid aldehyde) was prepared by modifying the procedure described in Synthesis B4 (i) to give the expected material which was recrystallized from ethanol and then had a melting point of 72-74 ° C. .

(ii) 4-Nitro-γ-chlorocinnamylidenemalonic acid was prepared by reaction of 80 g (0.39 mol). of 4-nitro- / 3-chloro-cinnamic acid aldehyde with 41 g (0.4 mol) of malonic acid in 50 ml of glacial acetic acid for 6 hours at 100 ° C. The cooled solution was poured into a 10% aqueous sodium hydroxide solution (300 mL), the alkalized portion was extracted with ether, and the aqueous portion was acidified by the addition of 300 mL of 30% aqueous hydrochloric acid. This gives 10.45 g of the expected product, m.p. 173-175 ° C.

Synthesis · C 1

Cinnamylidene-α-cyanoacetic acid is prepared by reacting 252 ml · (2.0 mol) of cinnamic aldehyde with azeotropically dried cyanoacetic acid (170 g, 2.0 mol) in 50 ml of glacial acetic acid for 2 hours · temperature 100 ° C. After addition of 130 ml of toluene, water is distilled off azeotropically within 5 hours, the toluene is distilled off, the reaction mixture is cooled, and the crystalline product is filtered off, washed with cold acetic acid and then with hot water to give 235 g of the expected Mp 210-212 ° C.

Synthesis of C 2

4-Chloro-α-phenyl cinnamic acid is prepared by reaction. 35 g (0.25 mol) of 4-chlorobenzaldehyde · 37.4 g (0.275 mol) of phenylacetic acid in 20 ml of glacial acetic acid at 100 ° C for 6 hours. After cooling, the product is filtered off, washed and dried to give 31.0 g of the expected compound, m.p. 204-206 ^° C.

Synthesis of C 3

4-Methyl-α-phenoxycinnamic acid is prepared by reacting 120 g (1 mol) of 4-methylbenzaldehyde with 167 g (1.1 mol) of phenylacetic acid in a mixture of 250 ml (2.5 mol) of acetic anhydride and 101 ml (1 mol) of triethylamine at 140 ° C for 5 hours. The dark red colored · solution · is poured into 5 liters · a mixture of 1 volume concentrated hydrochloric acid and 4 volumes water, the separated oil is separated, washed with water and then washed with a liter of 20% (w / v) sodium bisulfite solution · to give the crude product which is filtered off, washed and recrystallized from aqueous ethanol to give 22 g of the expected compound, m.p. 188-190 ° C.

Synthesis of C 4

4-Azido-α-cyanocinnamic acid was prepared using the procedure described in Example 3 of British Patent Specification No. 1,377,747; mp 160-161 ° C (dec.).

Synthesis C 5

Cinnamylidenemalonic acid polyethyl ester is prepared by reacting 31.6 ml (0.2633 mole) of cinnamic aldehyde with 35.7 g (0.26 mole) of potassium salt of maleic acid ethyl ester in 5.5 ml of glacial acetic acid at 100 ° C for After cooling, the product is filtered off, washed with a small amount of glacial acetic acid, dissolved in water, extracted with ether and the aqueous phase is acidified with dilute hydrochloric acid. 25.3 g of the expected product are obtained.

Synthesis of C 6

3- (2-Furyl) acrylic acid was prepared using the procedure described in Org. Synth. Co-11. Vol. III., 425 (1955). Mp 140-141 ° C.

Synthesis of C 7

Α-Cyano-4-methylcinnamylideneacetic acid is prepared by reacting 49 g (0.33 mol) of benzylideneacetone with 38 g (0.33 mol) of ethyl cyanoacetate using a mixture of 5 g of ammonium acetate and 15 g of acetic acid in a catalyst. 250 ml benzene. The reaction mixture is heated to reflux, the resulting water is removed by azeotropic distillation for five hours, the cooled solution is washed with water, dried over anhydrous magnesium sulphate and the solvent is distilled off to give a yellow crystalline mass.

After addition of a solution of 7.0 g of potassium hydroxide in 350 ml of methanol, the reaction mixture is refluxed for 6 hours, cooled, poured into · 400 ml of a 30% hydrochloric acid solution and the precipitate formed is filtered from aqueous solution after filtration. ethanol. 12.34 g of the expected product are obtained.

Example 1 (i) Preparation of an alkali soluble photosensitive resin

5 g (0.032 mol) of the polymer prepared according to synthesis A1 were dissolved in 100 ml of 2-butanone, adding 9.17 g (0.042 mol) of cinnamylidenemalonic acid (synthesis B2) and 0.4 g of benzyltriethylammonium chloride. The reaction mixture is heated at 80 ° C for 5 hours. After cooling, the product precipitates by pouring into 2 liters of water. The resulting slightly yellowish and light-sensitive polymer is filtered off, and dried in a stream of air at 40 ° C to give 10.4 g. The acid number is 492.

(ii) Prepare the platen

A solution of 2 g of sensitive polymer! to light, in 100 ml of 2-butanone, is applied on a sheet of granular and anodized aluminum using a horizontal sphincter, then dried at 80 ° C for 2 minutes. After exposing the light-sensitive plate thus prepared to the effects of a xenon lamp (4000 W) over a negative for 2 minutes followed by immersion in 5.7% sodium metasilicate solution, a printing plate is obtained by which satisfactory copies can be obtained.

Example 2 (i) Preparation of an alkali soluble photosensitive resin

5 g (0.052 mol) of the polymer prepared according to synthesis A1 were dissolved in 100 ml of 2-butanone, further 10.78 g (0.41 mol) of 3-nitrocinnamylidenemalonic acid and 0.4 g of benzyltriethylammonium chloride were added, and the reaction mixture was Heat at 80 ° C for 4 hours. Next, 25.37 g (0.128 mol) of cinnamylidene-α-cyanoacetic acid (Synthesis C1) and 0.4 g of benzyltriethylammonium chloride are added, and the reaction mixture is heated for a further 2 hours. The cooled reaction mixture was diluted with an equal volume of 2-butanone, filtered, and the filtrate was poured into a liter of 1,1,1-trichloroethane to precipitate the polymer as a flaky yellow precipitate, which was filtered off, sucked dry and redissolved. in 100 ml acetone. This solution is poured into a mixture of 2 liters of water and 150 ml of concentrated hydrochloric acid, and the precipitated resin is filtered off, washed and dried to give the substance in a yield of 9.63 g, the expected product of Amax 317 nm and number acidity 446.3.

(ii) Prepare the platen

A mixture of 3 g of the aforesaid light-sensitive resin and 0.3 g of 2,6-diamsyl-4-phenylthiapyrilium perchlorate is dissolved in 100 ml of 2-butanone, the solution is filtered, and applied to a surface of an electrically grain sheet using a horizontal sphincter. and anodically treated aluminum; This results in the formation of a coating with a basis weight of 1 g / m 2. After drying at 80 ° C for 2 minutes, the resulting light-sensitive layer is exposed to a 4000 W xenon lamp from a distance of 65 centimeters in a printing frame in contact with the negative for 40 seconds. The exposed plate is developed by washing with 5.7% aqueous sodium metasilicate solution, rinsing with water and staining with a greasy color.

Example 3 (i) Preparation of an alkali soluble photosensitive resin

Using the procedure described in Example 2 ad (i), a reaction of 5 g (0.032 mol) of poly-2,3-sulfoglyl ester of methacrylic acid (see Synthesis A1) with cinnamylidenemalonic acid (see Synthesis B 2) was carried out using 8 .9 g (0.041 mol). The reaction takes 2 hours, followed by further reaction with 16.5 g (0.064 mol) of 4-chloro-alpha-Rice, a phenyl (C 2 synthesis) for 4 hours to prepare 10.5 g of the expected product y · _max 319 nm acid number 490.4.

(ii) Preparing the printing plate (a)

A mixture of 3 g of the above photosensitive resin and 0.3 g of 1: 1, 2-butanone is dissolved in 100 ml of 2-butanone, the solution is filtered and the filtrate is applied with a vortex to the surface of an electrically roughened and anodically treated sheet of aluminum to form a coating with a basis weight of 1 g / m 2. After drying, the photosensitive plate thus prepared is exposed for 40 seconds through a step wedge and developed as described in the example. 2 (ii). This gives a six-stage printing plate according to the 6-degree wedge used, fully cured and dyed.

(iii) Prepare the printing plate (b)

The procedure of Example 3 (ii) is repeated except that 0.06 g of crystal violet is added as a dye to the solution used to apply the coating. It has been shown that due to the presence of dye in the exposed light-sensitive coating layer, removal of uncured alkali-soluble surfaces is facilitated to produce a clearly defined, visible image whose contrast increases as development progresses.

Example 4 (i) Preparation of an alkali soluble photosensitive resin

Using the procedure described in Example 2 (i), 5 g [0.032 mole] of poly-2,3-epoxypropyl methacrylic acid ester is reacted with 10.78 g (0.41 mole) of 2-throcinnamylidenemalonic acid (synthesis B3). 2 hours, after which a further reaction with 16.25 g (0.064 moles) of 4-methyl-.alpha.-phenoxycinnamic acid (synthesis C 3) for 8 hours gives 8 g of the expected product at .lambda.max of 330 nm with an acid equivalent of 485; 2 and content

2.9% N.

(ii) Prepare the platen

A mixture of 3 g of the above light-sensitive resin and 0.3 g of eosin is dissolved in 100 ml of 2-butanone, and after filtration, the solution is applied to a sheet of electro-grain and anodically treated aluminum to form a light-sensitive plate. exposure for 2 minutes and further processing as described in Example 2 (ii). The result is a high quality printing plate.

Example 5 (i) Preparation of an alkali soluble photosensitive resin

Using the procedure described in Example 2 (i), a reaction of 5 g (0.032 mol) of poly-2,3-epoxypropyl methacrylic acid tester (Synthesis A 1) is carried out with 10.35 g - [0.041 mol) of χ- chlorinamylidene malonate (synthesis B4) for 3 hours, and after addition of 17.55 g (0.082 mol) of 4-azido-α-cyanocinnamic acid (synthesis C 4), further reaction for 3 hours. The expected mixed ester resin having an Amax of 327 nm and an acid number of 558.5 is obtained in a yield of 8.4 g, the nitrogen content being 1.95%.

(ii) Prepare the platen

3 g of the above photosensitive resin and 0.03 grams of eosin are dissolved in 100 ml of 2-butanone, and a light-sensitive plate is produced by applying the solution to a sheet of electro-crushed aluminum, which is exposed for 2 minutes and processed as follows. described in Example 2 (ii). The result is a high-quality printing plate.

Example 6 (i) Preparation of an alkali soluble photosensitive resin

Using the procedure described in Example 2 (i), the reaction of -5 g (0.032 mol of poly-2,3-epoxypropyl methacrylic acid ester (Synthesis A1) with 4-nitro-γ-chlorocinnamylidenemalonic acid [Synthesis B 5] 12.2 g (0.041 mol). The reaction was carried out for <5 hours and after addition of 9.68 g (0.039 mol) of cinnamylidenemalonic acid ethylhydrogen ester (synthesis C 5) for an additional hour. Obtained in 10,025 g of the desired mixed ester resin and _m ax 347 nm and an acid number of 493.4. The nitrogen content was 2.0%.

(ii) Prepare the platen

3 g of the above photosensitive resin and 0.3 g of eosin are dissolved in 100 ml of 2-butanone, and after filtration, the solution is applied to a sheet of electrically roughened and anodized aluminum. This gives a light-sensitive plate which is exposed and processed according to the procedure described in Example 2 (ii). The result is a high quality board.

Example 7 (i) Preparation of an alkali soluble photosensitive resin

Using the procedure described in Example 2 (i), 5 g (0.032 mol) of methacrylic acid poly-2,3-epoxypropyl ester (AI synthesis) was reacted with 8.94 g (0.041 mol) of cinnamylidenemalonic acid [synthesis

B2) for 2 hours and then with 9.16 g (0.126 mol) of acrylic acid for an additional hour. 12.15 g of the expected mixed ester resin having an acid number of 501.0 are obtained.

(ii) Prepare the platen

3 g of the above photosensitive resin and 0.3 g of eosin are dissolved in 100 ml of 2-butanone, and the solution is applied to a sheet of electrically roughened and anodically treated aluminum after filtration. The resulting light-sensitive plate is exposed for a minute and processed further as described in Example 2 (ii) to produce a high-quality printing plate.

Example 8 (i) Preparation of an alkali soluble photosensitive resin

Using the procedure described in Example 2 (i), a reaction of 5 g (0.029 mol) of a poly-2,3-ethoxypropyl-pentyl-styrene copolymer (Synthesis A 4) with 8.28 g (0.038 mol) of cinnamylidenemalonic acid ( B2) for 2 hours, and 17.4 g (0.176 mole) of (2-mole) acrylic acid were added for an additional hour. The expected mixed ester resin having an acid number of 469.8 is obtained in a yield of 10.6 g.

(ii) Prepare the platen

3 g of the above are dissolved in 100 ml of 2-butanone. said photosensitive resin and 0.3 g of eosin, the solution is filtered and the filtrate is applied using a sphincter to a plate of electrically roughened treated aluminum to form a light-sensitive plate which is exposed for one minute and processed further as in of Example 2 (ii). The result is a high quality board.

Example 9 (i) Preparation of an alkali soluble photosensitive resin

Using the procedure described in Example 2 (i), 5 g (0.034 mol) of poly (2,3-epoxy) propyl acrylate copolymer with nitrile acrylic acid (synthesis A5) is reacted with 8.28 g (0.038 mol) Cinnamylidene malonic acid (synthesis B - 2) over a period of 0 hours and addition of 16.19 g - (0.076 mole) of α-cyano-β-α (1,3,6-mol) acid. ^ i ^ flnamylídenoctavé (synthesis C7) for further 2 hours to give 9.8 g of the desired mixed ester resin and about 32.1 _m ax. nm. and -o. acid number 531.1.

(ii) Prepare the platen

In 100 ml of 2-butanone, 3 g of the above-mentioned phthatensitive resin is dissolved and 0.3 g of the solution is filtered and the filtrate is applied to a sheet of electrically roughened and anodized aluminum with a sphincter. Drying gives a light-sensitive plate which is exposed as described in Example 2 (ii). The exposed plate is then cut into 3 equal parts. The first part is treated with 5.70 / ₀ aqueous sodium metasilicate solution and stained with water. Another portion is treated in 2.5% aqueous sodium hydroxide solution, and after rinsing with water, the third part is treated in 0.033 mol of trisodium phosphate solution and after rinsing is stained. All 3 parts of the board have similar print capability.

Example 10 (i) Preparation of an alkali soluble photosensitive resin

Reaction of 5 g (0.028 mol) of methacrylic acid poly-2,3-epoxypropyl ester copolymer with methacrylic acid dodecyl ester (synthesis A3) with 13.74 g (0.063 mol) of cinnamylidenemalonic acid (synthesis 22) for 6 hours at 80 ° C, 0.125 ml of triethylamine was used as catalyst. The homoester was isolated using the procedure described in Example 1 (i) to give 8.8 g of the product with an acid number of 461.6.

(ii) Prepare the platen

3 g of the above photosensitive resin and 0.3 g of eosin are dissolved in 100 ml of 2-butanone, the solution is filtered and the filtrate is applied to a sheet of electrically roughened and anodized aluminum. This results in a light-sensitive plate which is exposed for a minute and developed using a 5.7% aqueous sodium metasilicate solution. Upon rinsing with water, a hydrophobic image-forming space is formed which is capable of receiving color as a result of the addition of dodecyl ether of methacrylic acid to the polymer chain in the substrate. The printing plate has excellent printing properties.

Example 11 (i) Preparation of an alkali soluble photosensitive resin

Using the procedure described in Example 2 (i), 5 g (0.032 mol) of methacrylic acid poly-2,3-epoxypropyl ester (Synthesis A1) is reacted with 8.94 g (0.041 mol) of cinnamylidenemalonic acid (Synthesis V2) for 2 hours and then after addition of 18.14 g (0.126 mol) of octanoic acid, a further reaction for 4 hours yields 10.8 g of the expected mixed ester resin having an acid number of 613.6.

(ii) Prepare the platen

The printing plate is prepared according to the procedure described in Example (ii) and has been shown to have similar properties due to the incorporation of the octanoic acid ester group into the photosensitive resin.

Example 12 (ij) Preparation of an alkali soluble photosensitive resin

5 g (0.032 mol) of methacrylic acid poly-2,3-epoxypropyl ester (Synthesis A 1) and 0.2 g of benzyltriethylammonium bromide are dissolved in 100 ml of 2-butanone and after addition of 0.29 g (0.0032 mol) of the acid chloride propionic, the reaction mixture was heated at 80 ° C for 1 hour. Further, 13.74 g (0.063 mol) of cinniamylidenemalonic acid and 0.4 g of benzyltriethylammonium bromide are added, and the reaction mixture is heated for an additional 5 hours, after which the product is isolated using the procedure described in Example 2 (i) to give 9. 1 g of the expected mixed ester resin having an acid number of 422.9 and a chlorine content of 1.97% (w / w).

(ii) Prepare the platen.

This plate was prepared according to the procedure of Example 10 (ii). Numerous compliant copies can be made without hint of abrasion.

Example 13 (i) Preparation of an alkali soluble photosensitive resin.

Using the procedure described in Example 2 (i), 5 g (0.038 mol, calculated on epoxy groups) of poly-2,3-epoxypropyl acrylic acid ester (Synthesis A 2) is reacted with 17.0 g (0.075 mol) of Cinnamylidenemalonic Acid. 2.5 hours, and then 8.9 ml (9.388 g, 0.156 mol) of acetic acid was added for another 3.5 hours. 10.5 g of the expected mixed ester resin having an acid number of 443.1 are obtained.

(ii) Preparing the printing plate (a)

The printing plate was prepared according to the procedure described in Example 4 (ii). Numerous high-quality prints can be reproduced from it without hints of image abrasion.

(iii) Prepare the printing plate (b)

A portion of the light-sensitive plate prepared as described hereinbefore was exposed for 15 minutes with a 2150 W tungsten lamp at a distance of 0.5 m, whereupon the plate was developed and stained using the procedure described in Example 2 (ii); the result is a high quality printing plate.

(iv) Print plate preparation (c)

Another piece of light-sensitive plate, as prepared above, is exposed with an argon laser in the ultraviolet region - at 50 milljoules per cm · ² resulting in a high quality printing plate.

Example 14 (i) Preparation of an alkali soluble photosensitive resin

Using the procedure described in Example 2 (1), 15- g (0.096 mol) of methacrylic acid poly-2,3-epoxypropyl ester (Synthesis A) is reacted with 26.8 g · (0.123 mol) of cinnamylidenemalonic acid ( synthesis B2) for 4 hours and addition of 30 g (0.18 mol) of -trichloroacetic acid for a further 2 hours. The result is 31 g of the expected mixed ester having an acid number of 544.1.

(ii) Prepare the platen

The printing plate was exposed using the procedure described in Example 4 (ii). High quality copies can be made from it.

Example 15 (i) Preparation of an alkali soluble photosensitive resin.

10 g of the product of Example 14 are dissolved in 100 ml of 2-butanone and treated with 0.23 g (0.00225 mol) of acetic acid anhydrides for 4 hours to give 9.8 g of acetylated product.

(ii) Print plate preparation

A printing plate was prepared using the procedure of Example 4 (ii). It has an extremely hydrophobic sheet metal image, and can be made from it numerous copies without a hint of abrasion.

Claims (8)

Photopolymerizable material, characterized in that it is composed of a polymer comprising structural units of the general formula (I) R ¹ AND -C-CH ₂ - C = O AND O AND AND CH2 7'1 · - ' CH — Z R5 - - I. I ·. ·: '· CH 2 -O-C-C-C- (CR 4 = CR 3) and R 2. . -. II. <- ^; · · <.-. o cooh ..... · · · · · · · · · · · ^; :. ·. ··. ·· r (I) in which R ¹ represents -atom-hydrogen- or -methyl, R ² signify hydrogen atom · ·, alkylovou- group, - - optionally - substituted by a - chloro - or - -aryl - - -alkoxy or - a- .mající- 1 -to. - 10 - - carbon atoms, -aryl, optionally substituted with -, - halogen- or, alkyl or -alkoxy, and having 6 to 10 carbon atoms, or -heterocyclic-group, optionally substituted with -halogen , -alkyl, aryl or alkoxy and having 3 to 9 carbon atoms, R 3, R 4 - and - R 5, which may have the same or different meanings, mean a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, (C 1 -C 10) alkoxy, (C 6 -C 10) -aryloxy, (C 7 -C 20) aralkyl, (C 7 -C 20) -alkoxy, or C 2 -C 11 alkoxycarbonyl, Z represents a hydroxyl group or an ester group derived from an aliphatic, aromatic or heterocyclic carboxylic acid, a halide thereof or an anhydride thereof; 2, Photopolymerizable material. according to claim 1, characterized in that it is composed of a polymer comprising structural units of the general formula - 1 in which:. - - R-represents phenyl ² - group and R 3, -R 4 -and -R 5 are -hydrogen, or R ² is a 2-nitrophenyl group and R 1, R 4 and r 5 are hydrogen, or R ² represents a 3-nitrophenyl group and R 1, R 4 and R 5 represent a hydrogen atom, or -IR ² represents a phenyl group, R '- means a chlorine atom - and R 4 and R 5 represent a hydrogen atom, or R ² represents - 4-nitrophenyl, R '- means a chlorine atom and R4 and R5 are hydrogen. Photopolymerizable material according to Claims 1 and 2, characterized in that it consists of a polymer - containing - also structural units of the general formula II R ¹ —C — CH2 — 1 c = o 1 0 1 CH2 — CH 1 Z ¹ 0 R ⁵ СН2 — О — С — С = С— (CR ⁴ —CR ³ ) _b —R ² AND R ⁶ (II) wherein Z ¹ represents a hydroxyl group, a halogen atom or an ester group derived from an aliphatic, aromatic or heterocyclic carboxylic acid, its halide or anhydride, R ¹ represents hydrogen or methyl, R ² represents a hydrogen atom, an alkyl group optionally substituted by a halogen atom or an aryl group or an alkoxy group and having 1 to 10 carbon atoms, an aryl group optionally substituted with a halogen atom or • an alkyl group or an alkoxy group and having 6-10 carbon atoms or heterocykliokou a group optionally substituted by a halogen atom, an alkyl group, an aryl group or an alkoxy group and having 3 to 9 carbon atoms, R ³ , R ⁴ , R ⁵ and R ⁶ , which may have the same or different meanings, represent a hydrogen atom, a halogen atom, a cyano group, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group C 1 -C 10 aryloxy, C 6 -C 10 aryloxy, C 7 -C 20 aralkyl, C 7 -C 20 aralkoxy, or C 2 -C 11 alkoxycarbonyl, and b is 0 or 1 . 4. A photopolymerizable material as claimed in claim 3, wherein said photopolymerizable material is a polymer comprising structural units of formula (II) wherein b is 0 and R ² , R ⁵ , R ⁶ are hydrogen or b is 0, R ² and R ⁵ represent a hydrogen atom and R ⁶ represents a methyl group, or b represents 0, R ² is phenyl and R ⁵ and R ⁶ are hydrogen, or b is 0, R ² represents a 4-methoxyphenyl group, R ⁵ represents a hydrogen atom and R ⁶ represents a cyano group, or b represents 0, R ² is 4-chlorfenyIovou group, R ⁵ represents a hydrogen atom and R ⁶ represents a phenyl group, or b represents 0, R ² is 4-methylphenyl, R ⁵ represents a hydrogen atom and R ⁶ represents a phenoxy group, or b represents 0, R ² is 4-azldofenylovou group, R ⁵ represents a hydrogen atom and R ⁶ represents a cyano group, or b represents 0, R ² is 2-furyl, and R ⁵ and R ⁶ are hydrogen, or b is 1, R ² represents a phenyl group, R ³ , R ⁴ and R ⁵ are hydrogen and R ⁶ represents a cyano group, or b represents 1, R ² represents a phenyl group, R ³ , R ⁴ and R ⁵ are hydrogen and R ⁶ represents an ethoxycarbonyl group, or b represents 1, R ² represents a phenyl group, R ³ and R ⁴ are hydrogen, R ⁵ represents a methyl group and R ⁶ represents a cyano group. Photopolymerizable material according to one of Claims 1 to 4, characterized in that it consists of a polymer also containing structural units of the general formula III R ¹ —O-CH2— I c = o o CH2 AND CH-Z ¹ AND CH 2 —O — C — R ⁷ II o (ni) in which R ¹ represents hydrogen or methyl, Z ¹ represents a hydroxyl group, a halogen atom or an ester group derived from an aliphatic, aromatic or heterocyclic carboxylic acid, its halide or anhydride, and R 7 represents an alkyl group optionally substituted by a halogen atom or an aryl or alkoxy group having 1 to 10 carbon atoms, an aryl group optionally substituted by a halogen atom or an alkyl or alkoxy group having 6 to 10 carbon atoms, or a heterocyclic group optionally substituted a halogen atom or an alkyl group, an aryl group or an alkoxy group and having 3 to 9 carbon atoms. 6. A photopolymerizable material as claimed in claim 5, characterized in that it consists of a polymer comprising structural units of the general formula (III) in which: R ⁷ represents a methyl group and Z 1 represents a hydroxyl group, or R 7 represents a heptyl group and Z 1 represents a hydroxyl group, or R7 is ethyl and Z1 is -atom · chlorine, or R 7 is trichloromethyl and Z ¹ is hydroxyl. 7. A photopolymerizable material as claimed in any one of claims 1 to 6, characterized in that it is a polymer comprising also structural units derived from another unsaturated addition polymerizable monomer. Photopolymerizable material according to claim 7, characterized in that it consists of a polymer comprising units derived from methacrylic acid dodecyl ester, styrene or acrylic nitrile.